EP3445804B1 - Procédé pour faire passer des réacteurs d'une production de polyol catalysée par une base à une production de polyol catalysée par un cmd - Google Patents

Procédé pour faire passer des réacteurs d'une production de polyol catalysée par une base à une production de polyol catalysée par un cmd Download PDF

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EP3445804B1
EP3445804B1 EP17725799.5A EP17725799A EP3445804B1 EP 3445804 B1 EP3445804 B1 EP 3445804B1 EP 17725799 A EP17725799 A EP 17725799A EP 3445804 B1 EP3445804 B1 EP 3445804B1
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reactor
starter
catalyzed
dmc
mixture
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EP3445804A1 (fr
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Peter UTHE
Jack R. Reese
Stephen Bailey
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Covestro LLC
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Covestro LLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2669—Non-metals or compounds thereof

Definitions

  • Polyether polyols are used in the polyurethane industry for the production of polyurethane products such as coatings, sealants, adhesives, elastomers, and foams.
  • the industrial production of polyether polyols generally involves two alternative reactions - either the base-catalyzed oxyalkylation of starter molecules or the double metal cyanide (DMC)-catalyzed oxyalkylation of starter molecules.
  • the base and DMC catalysts used for the production of polyether polyols are incompatible because base catalysts deactivate DMC catalysts.
  • base-catalyzed polyol production and DMC-catalyzed polyol production generally require separate and dedicated production reactors to avoid cross-contamination of base compounds in DMC-catalyzed reaction mixtures. This can increase the cost of polyether polyol production and result in reactor under-utilization.
  • An alternative is washing the reactor with polyol, solvent, water and/or an acidic solution when switching between base-catalyzed and DMC-catalyzed technologies in the same reactor. This creates significant waste from the wash that must be properly treated and disposed of, which increases production costs.
  • the reactor must also be thoroughly dried to remove any trace solvent and/or water remaining in the reactor as these trace contaminants can decrease the activity of the DMC-catalyzed reaction and contribute to undesirable volatile organic compounds (VOCs) in the polyether product. Therefore, an improved process for switching between the base-catalyzed reaction and the DMC-catalyzed reaction is necessary.
  • EP 1577334 A1 relates in general to catalysis, and more specifically, to the acidification of starter feed stream(s) in a continuous addition of starter (CAOS) polyether polyol production process to improve double metal cyanide (“DMC”) catalyst activity.
  • CAOS starter polyether polyol production process
  • DMC double metal cyanide
  • EP 1528073 A1 relates in general to catalysis and more particularly to processes for preparing polyols within a single reactor by catalyzing an intermediate with a double metal cyanide (DMC) complex catalyst and base-catalyzing an ethylene oxide (EO)-cap.
  • DMC double metal cyanide
  • EO ethylene oxide
  • the inventive processes do not require removal of catalyst residues from the reactor prior to feeding the starter charge for the next polyol batch or of salts formed by the neutralization of the basic catalyst.
  • Polyols made by the inventive processes have a high content of primary hydroxyl groups and intrinsically low levels of unsaturation.
  • US 2013/338331 (A1 ) relates to methods for the preparation of polyether polyols by DMC-catalysed alkylene oxide addition to starter compounds comprising acidic sulfuric acid salts, to the use thereof for the preparation of polyurethanes, and to polyurethanes comprising the polyether polyols according to the invention.
  • This specification describes a process for transitioning a reactor from base-catalyzed polyol production to DMC-catalyzed polyol production.
  • the process comprises conducting a base-catalyzed polyol production reaction in a reactor, thereby producing a base-catalyzed product mixture.
  • the base-catalyzed product mixture is discharged from the reactor without being neutralized.
  • a starter mixture is then added to the reactor.
  • the reactor is not washed-out or rinsed between the discharging of the base-catalyzed product mixture and the addition of the starter mixture.
  • the starter mixture is added in an amount that contacts at least 12.5% of the total internal surface area of the reactor.
  • the starter mixture comprises a polyether polyol starter, a DMC catalyst, and 500-1200 ppm acid based on the total weight of the starter mixture.
  • a DMC-catalyzed polyol production reaction is then conducted in the reactor.
  • the process described in this specification eliminates the need for separate production reactors dedicated to either base-catalyzed polyol production or DMC-catalyzed polyol production.
  • the process facilitates the direct transition of a single reactor between the two reaction modes, without any intermediate washing of the reactor, cleaning of the reactor, rinsing of the reactor, or otherwise processing the reactor to remove residual base-catalyzed product after the un-neutralized product is discharged from the reactor, and without deactivation of the DMC catalyst from base or alkaline hold-up in the residual base-catalyzed product. inefficiently uses reactor time.
  • the processes comprises the addition of 500-1200 ppm of an acid to a DMC catalyst starter mixture, based on the total weight of the starter mixture, and adding the acidified starter mixture to the alkaline-contaminated reactor in an amount that contacts at least 12.5% of the total internal surface area of the reactor.
  • the acid added to the catalyst starter mixture must contact residual base-catalyzed product mixture in the reactor in order to effectively neutralize the residual base compounds and prevent DMC catalyst deactivation.
  • DMC catalyst starter mixture comprising 500-1200 ppm of an acid based on the total weight of the starter mixture is added to the reactor in an amount that contacts at least 12.5% of the total internal surface area of the reactor.
  • DMC catalyst starter mixture comprising 500-1200 ppm of an acid
  • a sufficient amount of the residual base-catalyzed product mixture will contact the acidified starter mixture to effectively neutralize the residual base and prevent the alkaline deactivation of the DMC catalyst.
  • the DMC catalyst starter mixture generally comprises: (a) a polyether polyol starter; (b) a DMC catalyst; and (c) 500-1200 ppm acid based on the total weight of the starter mixture.
  • the polyether polyol starter may comprise polyoxypropylene polyols, polyoxyethylene polyols, polytetatramethylene ether glycols, propoxylated glycerols, alkoxylated allylic alcohols, and combinations of any thereof.
  • polyether polyol starter may comprise a polyoxypropylene triol having a hydroxyl number in the range of 200-300 mg KOH/g.
  • the polyether polyol starter may be prepared using conventional polyether polyol production processes known in the art.
  • DMC catalysts suitable for use in the present process are described in U.S. Patent Nos. 3,427,256 ; 3,427,334 ; 3,427,335 ; 3,829,505 ; 4,472,560 ; 4,477,589 ; 5,158,922 ; 5,470,813 ; 5,482,908 ; 5,545,601 , 6,689,710 ; and 6,764,978 .
  • the DMC catalyst may comprise a zinc hexacyanocobaltate compound prepared, for example, as described in U.S. Pat. No. 5,482,908 .
  • the DMC catalyst may be present in the starter mixture in an amount comprising 30-100 ppm of the total weight of the final product, or any sub-range subsumed therein, such as, for example, 30-90 ppm or 60-90 ppm.
  • Acids suitable for use in the present process include mineral acids, organic carboxylic acids, phosphonic acids, and sulfonic acids.
  • phosphoric acid is a suitable mineral acid, including monosodium phosphate and monopotassium phosphate salts of phosphoric acid
  • acetic acid is a suitable organic acids.
  • mineral acids which may be suitable also include hydrochloric acid, hydrobromic acid, and sulfuric acid, among others, while suitable carboxylic acids or their acidifying derivatives also may include formic acid, oxalic acid, citric acid, maleic acid, maleic anhydride, succinic acid, succinic anhydride, adipic acid, adipoyl chloride, adipic anhydride, and the like.
  • the acid may be present in the starter mixture in an amount comprising 500-1200 ppm of the total weight of the starter mixture, or any sub-range subsumed therein, such as, for example, greater than 500 ppm to less than 1200 ppm, 500-1100 ppm, 500-1000 ppm, 500-900 ppm, 500-800 ppm, 500-700 ppm, 550-1200 ppm, 550-1100 ppm, 550-1000 ppm, 550-900 ppm, 550-800 ppm, 550-700 ppm 600-1200 ppm, 600-1100 ppm, 600-1000 ppm, 650-1000 ppm, 700-1000 ppm, 750-1000 ppm, or 800-1000 ppm.
  • the starter mixture comprising the polyether polyol starter; the DMC catalyst; and the acid may be added to the reactor in an amount that contacts at least 12.5% of the total internal surface area of the reactor including an external recirculation loop, if present.
  • the starter mixture may be added to the reactor in an amount that contacts at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, or at least 50% of the total internal surface area of the reactor.
  • the starter mixture may be added to the reactor in an amount that contacts 12.5-95%, 12.5-75%, 12.5-50%, 25-75%, or 25-50% of the total internal surface area of the reactor including an external recirculation loop, if present.
  • the starter mixture may be added to a reactor as a single charge or multiple charges.
  • the starter mixture may be added to the reactor as a first charge comprising approximately half of the polyether polyol starter and the acid, and a second charge comprising the balance of the polyether polyol starter and the DMC catalyst.
  • Adding the starter mixture to the reactor as multiple charges can comprise the addition of two or more charges, wherein each charge comprises respective portions of the polyether polyol starter, the DMC catalyst, and the acid.
  • the starter mixture may be heated in the reactor to a temperature in the range of 100-200°C for 15-60 minutes before conducting the DMC-catalyzed polyol production reaction in the reactor.
  • the starter mixture may be heated in the reactor to a temperature in the range of 100-200°C or any sub-range subsumed therein, such as, for example, 130-150°C.
  • the starter mixture may be heated in the reactor for a time in the range of 15-60 minutes or any sub-range subsumed therein, such as, for example, 15-30 minutes.
  • a DMC-catalyzed polyol production reaction is conducted in the reactor.
  • Conducting the DMC-catalyzed polyol production reaction may comprise heating the starter mixture in the reactor to a temperature in the range of 100-200°C or any sub-range subsumed therein, such as, for example, 130-150°C.
  • Conducting the DMC-catalyzed polyol production reaction may further comprise applying a vacuum and a nitrogen sparge to the reactor, sealing the reactor under vacuum, and activating the DMC catalyst by adding an initial charge of an alkylene oxide to the reactor.
  • an alkylene oxide such as propylene oxide, ethylene oxide, or combinations thereof, may be added to the reactor.
  • the initial activating charge of the alkylene oxide may comprise 4-8% based on the total weight of the alkylene oxide and the starter mixture.
  • the activation time of the DMC catalyst (defined as the time required for the reactor pressure to drop by 50% of the maximum pressure reached during the addition of the initial activating charge of the alkylene oxide) may be less than 60 minutes, less than 45 minutes, less than 30 minutes, less than 25 minutes, less than 20 minutes, less than 15 minutes, or less than 10 minutes.
  • the starter mixture may comprise zero alkalinity and an acid number of less than 0.20 mg KOH/g, less than 0.15 mg KOH/g, less than 0.10 mg KOH/g, or less than 0.05 mg KOH/g.
  • the DMC-catalyzed polyol production reaction may be conducted with a build ratio of less than 8.
  • the build ratio of a polyol production reaction is the ratio of the number average molecular weight of the polyol product produced in the reaction to the number average molecular weight of the polyether polyol starter used in the reaction or the ratio of the final product weight to the starter weight. Higher build ratios correspond to lesser amounts of starter mixture in the reactor, and lower build ratios correspond to greater amounts of starter mixture in the reactor.
  • the build ratio should be sufficiently low to ensure that the starter mixture contacts at least 12.5% of the internal surface area of reactor when added to the reactor and before catalyst activation.
  • the DMC-catalyzed polyol production reaction may be conducted, for example, with a build ratio of less than 12, less than 10, less than 8, less than 7, less than 6, less than 5, or less than or equal to 4.
  • Conducting the DMC-catalyzed polyol production reaction may comprise conducting a semi-batch process, wherein an alkylene oxide (e.g. , propylene oxide) is continuously added to the reactor during the DMC-catalyzed polyol production reaction.
  • Conducting the DMC-catalyzed polyol production reaction may comprise conducting a continuous addition of starter (CAOS) process, wherein an alkylene oxide and additional starter are continuously added to the reactor during the DMC-catalyzed polyol production reaction.
  • CAOS continuous addition of starter
  • a base-catalyzed polyol production reaction and the resulting base-catalyzed product mixture were simulated by charging an 8 gallon continuously stirred tank reactor with 5 gallons of a mixture comprising a polyoxypropylene triol having a hydroxyl number of 56 mg KOH/g and 0.33% potassium hydroxide by total weight of the polyoxypropylene triol and potassium hydroxide ("base-catalyzed product simulant").
  • base-catalyzed product simulant was stirred and heated in the reactor at a temperature of 100°C for 60 minutes.
  • the un-neutralized base-catalyzed product simulant was then discharged from the reactor with a nitrogen purge at 60°C for 20 minutes.
  • a starter mixture was added to the discharged reactor in an amount sufficient to provide a build ratio of 8.5 (2414 grams).
  • the reactor was not washed, rinsed, or otherwise processed to remove residual base-catalyzed product simulant after discharging from the reactor.
  • the starter mixture comprised a polyether polyol starter (polyoxypropylene triol, hydroxyl number in the range of 233-243 mg KOH/g), 30-120 ppm of a zinc hexacyanocobaltate DMC catalyst based on the total weight of the final product, and 0 to 1000 ppm of phosphoric acid based on the total weight of the starter mixture.
  • the starter mixture was heated in the reactor to 130°C with a nitrogen purge under vacuum for 30 minutes.
  • the reactor was then heated to a reaction temperature of 130-150°C, the reactor was sealed under the vacuum, and 4 to 10% propylene oxide was added to the sealed vacuum (by total weight of the starter mixture) to activate the DMC catalyst. If the catalyst did not initially activate a second charge of propylene oxide was added to assist in the catalyst - this activation amount, if used, did not exceed 12%.
  • the activation time of the DMC catalyst was measured as the time required for the reactor pressure to drop by 50% of the maximum pressure reached during the addition of the propylene oxide.
  • the activation time is a measure of the activity of the catalyst - the shorter the activation time the more active the catalyst.
  • the reactor was maintained at a reaction temperature of 130-150°C and propylene oxide was added continuously over about 6.5 hours, after which the propylene oxide feed was discontinued (semi-batch operation, 18105 total grams of propylene oxide fed - activation + steady feed).
  • the maximum pressure during the steady oxide feed was typically reached at the end of the oxide feed - this is documented as the peak pressure below.
  • the peak pressure provides a measure of the activity of catalyst during the oxide feed - the higher the peak pressure the less active the catalyst.
  • the reactor contents were maintained at a reaction temperature of 130-150°C for 0.5 hours. Vacuum was then applied to the reactor to remove unreacted propylene oxide, and thereafter the DMC-catalyzed product was cooled and discharged from the reactor.
  • the DMC-catalyzed product comprised a polyoxypropylene triol having a hydroxyl number of about 28 mg KOH/g.
  • Table 1 Comparative Examples at Acid Levels in Starter ⁇ 500 ppm.
  • ND No Data. Table 2. Comparative Examples at Acid Levels in Starter ⁇ 500 ppm. Example 5 6 7 8 9 10 11 Catalyst Concentration (ppm) 30 30 30 60 60 60 60 60 Acid Added to Starter (ppm) 250 250 250 (95/5)** 250 250 (75/25)** 250 (50/50)** 250 Activation Temperature (°C) 140 130 140 140 140 140 140 140 Wt% PO for Activation (based on starter weight) 4 4 4 4 4 / 8* 4 4 / 8* 8 Activation Time (min) 5 14 10 >150 50 66 6 Peak Pressure (PSIA) 51 72 52 NR 13.8 13.4 13.5 Hydroxyl Number (mgKOH/g) 27.7 27.9 27.8 ND 28 28 28.6 Viscosity (cks @ 25°C) 2657 1695 2749 ND 1340 1334 1695 Molecular Weight Distribution (Mw/Mn) 1.372 1.123 1.335 ND 1.069 1.072 1.053 *4% activation charge was
  • Example 12 13 14 15 16 Catalyst Concentration (ppm) 90 120 120 120 120 Acid Added to Starter (ppm) 250 250 250 250 250 250 250 Activation Temperature (°C) 140 140 140 150 150 Wt% PO for Activation (based on starter weight) 4 / 8* 4 4 10 10 Activation Time (min) >120 35 35 4 13 Peak Pressure (PSIA) NR 13.6 13.2 11.8 22.4 Hydroxyl Number (mgKOH/g) ND 28.1 28.1 28 28.3 Viscosity (cks @ 25°C) ND 1254 1248 1255 1375 Molecular Weight Distribution (Mw/Mn) ND 1.057 1.047 1.059 1.145 *4% activation charge was followed by second charge of 8%. NR No Reaction.
  • ND No Data. Table 4.
  • Example 23 (90 ppm catalyst, 500 ppm phosphoric acid, 140°C reaction temperature, 4% PO added for activation) was repeated, except, instead of adding the starter mixture to the reactor without washing, cleaning, rinsing, or otherwise processing the reactor to remove residual base-catalyzed product simulant after discharging from the reactor, 0.9% of the base-catalyzed product simulant was added to the starter mixture (by total weight of the starter mixture and the added based-catalyzed product simulant, 177 grams). The starter mixture comprising the 0.9% of the base-catalyzed product simulant was added to a clean reactor with no residual base-catalyzed product simulant from a prior base-catalyzed polyol production simulation.
  • the activation time of the DMC catalyst was 5 minutes and the reactor maintained typical pressure for DMC-catalyzed polymerization with a peak pressure of 13.9 psia.
  • the final product had a hydroxyl number of 27.9 mgKOH/g and a viscosity of 1379 cst at 25°C and a molecular weight distribution Mw/Mn of 1.092.
  • a starter mixture was added to the discharged reactor in an amount sufficient to provide a build ratio of 4 (4968 grams).
  • the reactor was not washed, rinsed, or otherwise processed to remove residual base-catalyzed product simulant after discharging from the reactor.
  • the starter mixture comprised a poly ether polyol starter (polyoxypropylene triol, hydroxyl number in the range of 233-243 mg KOH/g), 30-120 ppm of a zinc hexacyanocobaltate DMC catalyst based on the total weight of the final product, and 0 to 1000 ppm of phosphoric acid based on the total weight of the starter mixture.
  • the starter mixture was heated in the reactor to 130°C with a nitrogen purge under vacuum for 30 minutes.
  • the reactor was then heated to reaction temperature 130-150°C, the reactor was sealed under the vacuum, and 4 to 10% propylene oxide was added to the sealed vacuum (by total weight of the starter mixture) to activate the DMC catalyst. If the catalyst did not initially activate a second charge of propylene oxide was added to assist in the catalyst - this activation amount did not exceed 12%.
  • the activation time of the DMC catalyst was measured as the time required for the reactor pressure to drop by 50% of the maximum pressure reached during the addition of the propylene oxide.
  • the activation time is a measure of the activity of the catalyst - the shorter the activation time the more active the catalyst or the better that the base was neutralized.
  • the reactor was maintained at reaction temperature 130-150°C and propylene oxide was added continuously over about 6 hours, after which the propylene oxide feed was discontinued (semi-batch operation, 15551 total grams of propylene oxide fed - activation + steady feed).
  • the maximum pressure during the steady oxide feed was typically reached at the end of the oxide feed - this is documented as the peak pressure below.
  • the peak pressure provides a measure of the activity of catalyst during the oxide feed - the higher the peak pressure the less active the catalyst.
  • the reactor contents were maintained at reaction temperature 130-150°C for 0.5 hours. Vacuum was then applied to the reactor to remove unreacted propylene oxide, and thereafter the DMC-catalyzed product was cooled and discharged from the reactor.
  • the DMC-catalyzed product comprised a polyoxypropylene triol having a hydroxyl number of about 57.5 mg KOH/g.
  • Table 6 Examples at Build Ratio of 4 or 25% Starter in Reactor.
  • the addition of the acid to the starter mixture for the DMC-catalyzed polyol production reaction effectively neutralized the residual base-catalyzed product simulant remaining in the reactor, as evidenced by the activation of the DMC catalyst and the production of the DMC-catalyzed polyoxypropylene triol product.
  • the decrease of the build ratio from 8 (Examples 1-31) to 4 increased the internal surface area of the reactor contacted by the starter mixture from 12.5% to 25% of the total internal surface area of the reactor.
  • Examples 32-34 indicated that increasing acid concentration correlates with increasing catalyst activation time and that acid concentrations greater than about 1200 ppm can prevent DMC catalysts from activating.
  • the DMC catalyst activated in examples 32 and 33 and the reaction proceeded to completion, producing a DMC-catalyzed polyoxypropylene triol product having a hydroxyl number of about 56 mg KOH/g.
  • Examples 35-38 are similar to Examples 32-34 above with the exception that one liter of crude alkaline polyol containing 0.33% KOH, neutralized with phosphoric acid was added to the starter mixture ( ⁇ 3000 ppm phosphoric acid added to crude alkaline polyol for neutralization). The reactor was also subjected to the "based-catalyzed product simulant" before the starter mixture was added. Table 7. Examples at Build Ratio of 4 with 1L of Neutralized Polyol Added to Starter Mixture.
  • Example 35 36 37 38 Catalyst Concentration (ppm) 90 90 90 90 Acid Added to Starter (ppm) 0 500 500 750 Activation Temperature (°C) 140 140 140 140 Wt% PO for Activation (based on starter weight) 4 4 4 4 4 Activation Time (min) 15 14 19 16 Peak Pressure (PSIA) 65* 14.5 18.8 14.6 Hydroxyl Number (mgKOH/g) ND 52.8 52.9 57.3 Viscosity (cks @ 25°C) ND 604 632 723 Molecular Weight Distribution (Mw/Mn) ND 1.024 1.053 1.039 *Rapid pressure increase after restarting PO feed, run terminated due to high pressure.
  • Mw/Mn Molecular Weight Distribution
  • Examples 35-38 were designed to stress the reactor transition by simulating a large amount of residual base-catalyzed product mixture.
  • Example 35 did not include any acid added to the starter mixture (only the acid added to the 1L of residual base-catalyzed product simulant). While the catalyst quickly activated, the run deactivated before completion, likely due to the residual potassium hydroxide from the drained simulant that was not neutralized by the acid added to the additional 1L of residual base-catalyzed product simulant. This further indicates that catalyst activation is independent of the amount of residual base-catalyzed product simulant/mixture provided that the residual base is neutralized.
  • Examples 36-38 included additional acid added to the starter mixture and these runs had fast catalyst activation and proceeded to completion, producing a DMC-catalyzed polyoxypropylene triol product having normal product properties.
  • Examples 39-41 used an amount of starter mixture sufficient to provide a build ratio of 4 in an 80 gallon continuously stirred tank reactor (semi-batch operation). The reactor was not washed, rinsed, or otherwise processed to remove residual base-catalyzed product simulant after discharging from the reactor. In all cases the product simulant was a 60 OH# glycerin based all-PO polyol containing 0.34% KOH. Approximately 200 kg of this KOH containing material was circulated in the reactor at 105°C for 1 hour.
  • the scale-up reactor is equipped with a recirculation loop that includes a pump and heat exchanger.
  • the un-neutralized base-catalyzed product simulant was circulated through the recirculation loop and external heat exchanger.
  • the product simulant was discharged from the reactor after the hour mixing and recirculation time - no further cleaning or rinsing or neutralizing was done prior to charging the starter mixture.
  • the starter mixture was heated in the reactor to 130°C with a nitrogen purge under vacuum for 30 minutes.
  • the reactor was then heated to a reaction temperature of 130-150°C, the reactor was sealed under the vacuum, and 4 to 10% propylene oxide was added to the sealed vacuum (by total weight of the starter mixture) to activate the DMC catalyst. If the catalyst did not initially activate a second charge of propylene oxide was added to assist in the catalyst - this activation amount did not exceed 12%.
  • the activation time of the DMC catalyst was measured as the time required for the reactor pressure to drop by 50% of the maximum pressure reached during the addition of the propylene oxide. After activation, the reactor was maintained at a reaction temperature of 130-150°C and propylene oxide was added continuously over about 6 hours, after which the propylene oxide feed was discontinued (semi-batch operation). The maximum pressure during the steady oxide feed was typically reached at the end of the oxide feed - this is documented as the peak pressure below. The reactor contents were maintained at the reaction temperature of 130-150°C for 0.5 hours. Vacuum was then applied to the reactor to remove unreacted propylene oxide, and thereafter the DMC-catalyzed product was cooled and discharged from the reactor. Table 8.
  • Example 39 40 41 Catalyst Concentration (ppm) 90 90 90 Acid Added to Starter (ppm) 500 500 500 Activation Temperature (°C) 140 140 140 Wt% PO for Activation (based on starter weight) 4 4 8 Activation Time (min) 38 47 32 Peak Pressure (PSIA) 30 29 29 Hydroxyl Number (mgKOH/g) 56.2 56.6 56.5 Viscosity (cks @ 25°C) 542 548 552 Molecular Weight Distribution (Mw/Mn) 1.07 1.029 1.028
  • Example 41 the DMC-catalyzed polyoxypropylene triol product was discharged from the reactor, and a starter mixture was added to the discharged reactor in an amount sufficient to provide a build ratio of 8.
  • the reactor was not washed, rinsed, or otherwise processed to remove residual product from Example 41 after discharging from the reactor.
  • the starter mixture comprised a polyether polyol starter (polyoxypropylene triol, hydroxyl number in the range of 233-243 mg KOH/g), 30 ppm of a zinc hexacyanocobaltate DMC catalyst based on the total weight of the final product, and no added acid.
  • the reaction was conducted as described above in connection with Examples 39-41, and with the parameters shown in Table 9.
  • Example 42 Catalyst Concentration (ppm) 30 Acid Added to Starter (ppm) 0 Activation Temperature (°C) 130 Wt% PO for Activation (based on starter weight) 4 Activation Time (min) 32 Peak Pressure (PSIA) 35 Hydroxyl Number (mgKOH/g) 28 Viscosity (cks @ 25°C) 1300 Molecular Weight Distribution (Mw/Mn) 1.08
  • Example 43-54 A series of twelve polyol production reactions (Examples 43-54) were performed consecutively in an 8 gallon continuously stirred tank reactor. A based-catalyzed product simulant, as described above, was not used. Instead, Example 43 used a potassium hydroxide-catalyzed polyol production reaction. The product mixture of each example was discharged before the next example and the reactor was not washed, rinsed, neutralized or otherwise processed to remove residual product after discharging from the reactor. Examples 43-54 were performed with the parameters shown in Tables 10 and 11.
  • the base-catalyzed product mixture produced in Example 43 comprised 0.1% of potassium hydroxide by total weight of the base-catalyzed product mixture.
  • the base-catalyzed product mixtures produced in Examples 46, 48, 50, and 52 comprised 0.7% of potassium hydroxide by total weight of the base-catalyzed product mixture.
  • the base-catalyzed product mixtures were discharged from the reactor un-neutralized.
  • the starter mixtures included the starter compounds in an amount sufficient to provide the build ratios listed in Tables 10 and 11.
  • the polyether polyol starter in Examples 44, 45, 47, 49, 51, 53, and 54 was a polyoxypropylene triol having a hydroxyl number in the range of 233-243 mg KOH/g.
  • the starter mixtures for the DMC-catalyzed runs included 90 ppm of a zinc hexacyanocobaltate DMC catalyst.
  • the starter mixtures for the DMC-catalyzed runs also included phosphoric acid at the concentrations identified in Tables 10 and 11. The starter mixtures were added to the unwashed/unrinsed reactor.
  • the reactor was heated to 130°C with a nitrogen purge for 30 minutes in the DMC-catalyzed runs. The reactor was then heated to the activation temperatures listed in Tables 10 and 11, vacuum was applied to the reactor, and the reactor was sealed under the vacuum. The propylene oxide activator was added to the sealed reactor in the amount listed in Tables 10 and 11 to activate the DMC catalyst in the DMC-catalyzed runs. Table 10. Consecutive Reactor Transitions Varying KOH content and acid content (Examples 43-48). Example 43 44 45 46 47 48 Reactor Condition Clean Ex. 43 drained Ex. 43 product simulant Ex. 44 Ex. 46 Ex.
  • ND No Data. Table 11. Consecutive Reactor Transitions Varying KOH content and acid content (Examples 49-54).
  • Example 51 the addition of the acid to the starter mixture for the DMC-catalyzed polyol production reactions effectively neutralized the residual base-catalyzed product mixture remaining in the reactor, as evidenced by the activation of the DMC catalyst and the production of the DMC-catalyzed polyoxypropylene triol product.
  • These runs further demonstrate that a DMC-catalyzed polyol production reaction using a starter mixture comprising acid can successfully transition a reactor from base-catalyzed polyol production to DMC-catalyzed polyol production, without any intermediate washing, cleaning, or rinsing of the reactor, and produce poly ether polyols that meet product specifications.
  • the runs in these examples facilitate the development of a predictive model for the minimum amount of acid to be added to a starter mixture to successfully transition a reactor from base-catalyzed polyol production to DMC-catalyzed polyol production.
  • a starter mixture was added to the clean reactor in an amount sufficient to provide a build ratio of 4.
  • the starter mixture comprised a poly ether polyol starter (polyoxypropylene triol, hydroxyl number in the range of 233-243 mg KOH/g), 60 ppm of a zinc hexacyanocobaltate DMC catalyst based on the total weight of the final product, and varying amounts and types of acid, as shown in Tables 12-14.
  • the starter mixture was heated in the reactor to 130°C with a nitrogen purge for 30 minutes.
  • the reactor was then heated to 140°C, vacuum was applied to the reactor, the reactor was sealed under the vacuum, and 4% propylene oxide was added to the sealed vacuum (by total weight of the propylene oxide and the starter mixture) to activate the DMC catalyst.
  • the activation times of the DMC catalyst are reported in Tables 12-14. After activation, the reactor was maintained at 140°C for 0.5 hours. Vacuum was then applied to the reactor to remove unreacted propylene oxide, and thereafter the DMC-catalyzed activated starter mixture was cooled and discharged from the reactor. (An activation was only completed for these runs the reaction was not carried to completion) Table 12. Effect of acid concentration of DMC catalyst activation (Examples 55-60).
  • Example 55 56 57 58 59 60 Catalyst Concentration (ppm) 60 60 60 60 60 60 Acid Phosphoric acid Phosphoric acid Phosphoric acid Phosphoric acid Phosphoric acid Acid Added to Starter (ppm) 0 0 125 250 500 750 Activation Temperature (°C) 140 140 140 140 140 140 Wt% PO for Activation (based on starter weight) 4 4 4 4 4 4 4 Activation Time (min) 7 9 12 15 18 48 Table 13. Effect of acid concentration of DMC catalyst activation (Examples 61-66).
  • Example 67 68 69 70 71 72 73 Catalyst Concentration (ppm) 60 60 60 60 60 60 60 Acid acetic acid HCl HCl water sodium monophosphate sodium monophosphate sodium monophosphate Acid Added to Starter (ppm) 1000 1000 372 180 1000 1000 5000 Activation Temperature (°C) 140 140 140 140 140 140 140 140 Wt% PO for Activation (based on starter weight) 4 4 4 4 4 4 4 4 Activation Time (min) 14 NR 34 5 7 7 8 NR No Reaction
  • grammatical articles "one”, “a”, “an”, and “the”, as used in this specification, are intended to include “at least one” or “one or more”, unless otherwise indicated.
  • the articles are used in this specification to refer to one or more than one (i.e., to "at least one") of the grammatical objects of the article.
  • a component means one or more components, and thus, possibly, more than one component is contemplated and can be employed or used in an implementation of the described compositions and products.
  • the use of a singular noun includes the plural, and the use of a plural noun includes the singular, unless the context of the usage requires otherwise.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • Polyethers (AREA)

Claims (15)

  1. Procédé de transition d'un réacteur de la production de polyol catalysée par une base à la production de polyol catalysée par un double cyanure métallique (DMC), le procédé comprenant :
    (i) la conduite d'une réaction de production de polyol catalysée par une base dans un réacteur, de façon à produire un mélange de produits à catalyse basique ;
    (ii) l'évacuation du mélange de produits à catalyse basique depuis le réacteur, dans lequel le mélange de produits à catalyse basique n'est pas neutralisé avant d'être évacué du réacteur ;
    (iii) l'ajout d'un mélange d'amorceur au réacteur, dans lequel le réacteur n'est pas lavé ou rincé entre l'évacuation du mélange de produits à catalyse basique et l'ajout du mélange d'amorceur, dans lequel le mélange d'amorceur est ajouté en une quantité qui entre en contact avec au moins 12,5 % de la surface interne totale du réacteur, et dans lequel le mélange d'amorceur comprend :
    (a) un amorceur de polyéther polyol ;
    (b) un catalyseur de DMC ; et
    (c) 500 à 1200 ppm d'acide sur la base du poids total du mélange d'amorceur ; et
    (iv) la conduite d'une réaction de production de polyol catalysée par DMC dans le réacteur.
  2. Procédé selon la revendication 1, dans lequel le mélange d'amorceur est ajouté en une quantité qui entre en contact avec au moins 25 % de la surface interne totale du réacteur.
  3. Procédé selon la revendication 1, dans lequel la réaction de production de polyol catalysée par DMC est conduite avec un rapport de composition inférieur à 8, de préférence inférieur à 5.
  4. Procédé selon la revendication 1, dans lequel le mélange d'amorceur comprend 500 à 1000 ppm de l'acide sur la base du poids total du mélange d'amorceur.
  5. Procédé selon la revendication 1, dans lequel le mélange de produits à catalyse basique comprend plus de 0,33 % de base résiduelle en poids du mélange de produits à catalyse basique, et dans lequel le mélange d'amorceur comprend moins de 1200 ppm, de préférence un maximum de 1000 ppm, de l'acide et au moins Y ppm de l'acide sur la base du poids total du mélange d'amorceur, dans lequel : Y = 810,0 * X + 232,4 ;
    Figure imgb0006
     et
    dans lequel X est le pourcentage en poids de base résiduelle dans le mélange de produits à catalyse basique.
  6. Procédé selon la revendication 1, dans lequel le mélange d'amorceur comprend zéro alcalinité et un indice d'acide inférieur à 0,20 mg KOH/g, de préférence inférieur à 0,15 mg KOH/g, avant l'activation du catalyseur de DMC.
  7. Procédé selon la revendication 1, dans lequel le mélange d'amorceur comprend 60 à 90 ppm du catalyseur de DMC sur la base du poids total du mélange d'amorceur.
  8. Procédé selon la revendication 1, comprenant en outre le chauffage du mélange d'amorceur dans le réacteur à une température dans la plage de 130 à 150 °C pendant 15 à 60 minutes avant la conduite de la réaction de production de polyol catalysée par DMC dans le réacteur.
  9. Procédé selon la revendication 1, dans lequel le catalyseur basique comprend de l'hydroxyde de potassium.
  10. Procédé selon la revendication 1, dans lequel l'amorceur de polyéther polyol comprend un polyoxypropylène triol ayant un indice d'hydroxyle dans la plage de 200 à 300 mg KOH/g.
  11. Procédé selon la revendication 1, dans lequel l'acide comprend l'acide phosphorique.
  12. Procédé selon la revendication 1, dans lequel la conduite de la réaction de production de polyol catalysée par DMC dans le réacteur comprend le chauffage du mélange d'amorceur dans le réacteur à une température dans la plage de 130 à 150 °C, l'application d'un vide au réacteur, et l'activation du catalyseur de DMC par ajout de 4 à 8 % d'un oxyde d'alkylène au réacteur sur la base du poids total de l'oxyde d'alkylène et du mélange d'amorceur.
  13. Procédé selon la revendication 1, dans lequel le temps d'activation du catalyseur de DMC est inférieur à 30 minutes.
  14. Procédé selon la revendication 1, dans lequel la conduite de la réaction de production de polyol catalysée par DMC dans le réacteur comprend la conduite d'un procédé semi-discontinu, dans lequel un oxyde d'alkylène est ajouté en continu au réacteur pendant la réaction de production de polyol catalysée par DMC.
  15. Procédé selon la revendication 1, dans lequel la conduite de la réaction de production de polyol catalysée par DMC dans le réacteur comprend la conduite d'un processus d'ajout continu d'amorceur (CAOS), dans lequel un oxyde d'alkylène et de l'amorceur supplémentaire sont ajoutés en continu au réacteur pendant la réaction de production de polyol catalysée par DMC.
EP17725799.5A 2016-04-20 2017-04-18 Procédé pour faire passer des réacteurs d'une production de polyol catalysée par une base à une production de polyol catalysée par un cmd Active EP3445804B1 (fr)

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US15/133,819 US9994506B2 (en) 2016-04-20 2016-04-20 Process for transitioning reactors from base-catalyzed polyol production to DMC-catalyzed polyol production
PCT/US2017/028046 WO2017184550A1 (fr) 2016-04-20 2017-04-18 Procédé pour faire passer des réacteurs d'une production de polyol catalysée par une base à une production de polyol catalysée par un cmd

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CN113631629A (zh) * 2019-02-28 2021-11-09 陶氏环球技术有限责任公司 聚醚聚合工艺
CN114409889A (zh) * 2021-12-13 2022-04-29 山东一诺威新材料有限公司 减少dmc催化合成聚醚多元醇中高分子量部分拖尾的方法

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CN109071794A (zh) 2018-12-21
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US20170305826A1 (en) 2017-10-26
EP3445804A1 (fr) 2019-02-27
US9994506B2 (en) 2018-06-12

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